EP0047948B1 - Procédé pour la préparation de composés carbonyle polyfluorés et quelques représentants de cette famille de composés - Google Patents

Procédé pour la préparation de composés carbonyle polyfluorés et quelques représentants de cette famille de composés Download PDF

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Publication number
EP0047948B1
EP0047948B1 EP81107000A EP81107000A EP0047948B1 EP 0047948 B1 EP0047948 B1 EP 0047948B1 EP 81107000 A EP81107000 A EP 81107000A EP 81107000 A EP81107000 A EP 81107000A EP 0047948 B1 EP0047948 B1 EP 0047948B1
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Prior art keywords
formula
compounds
atoms
acid
mol
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EP81107000A
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German (de)
English (en)
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EP0047948A2 (fr
EP0047948A3 (en
Inventor
Hans Dr. Millauer
Günter Dr. Siegemund
Werner Dr. Schwertfeger
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Hoechst AG
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Hoechst AG
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C07C45/54—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition of compounds containing doubly bound oxygen atoms, e.g. esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C305/00—Esters of sulfuric acids
    • C07C305/26—Halogenosulfates, i.e. monoesters of halogenosulfuric acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/04—Saturated compounds containing keto groups bound to acyclic carbon atoms
    • C07C49/16—Saturated compounds containing keto groups bound to acyclic carbon atoms containing halogen
    • C07C49/167—Saturated compounds containing keto groups bound to acyclic carbon atoms containing halogen containing only fluorine as halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C59/185—Saturated compounds having only one carboxyl group and containing keto groups
    • C07C59/21—Saturated compounds having only one carboxyl group and containing keto groups containing halogen

Definitions

  • perfluorinated ketocarboxylic acid esters such as the esters of heptafluoroisopropylglyoxylic acid (CF 3 ) Z CFCOCOOH include valuable heat transfer fluids and surface-active agents which are distinguished by high chemical and thermal stability (JP-OS Sho-54-163521).
  • ketocarboxylic acid esters have generally been prepared from dicarbonyl compounds. This is how Zh. Org. Khim 13, 990 (1977) the reaction of perfluorodicarboxylic acid fluorides with perfluoroolefins: However, this process has the disadvantage that, in addition to the desired ketocarboxylic acid fluoride, which, for example, according to Zh. Org. Khim 11, 1626 (1975) can be esterified: the diketone is obtained in up to 30% yield. Perfluoroketocarbonyl compounds according to Zh. Org.
  • ketocarboxylic acid esters containing a CF 3 -CO group can be prepared by the previously mentioned methods. Trifluoromethyl ketones with an ester group have so far only been available by two special methods.
  • the object of this invention was to provide a simple process for the preparation of both known and new perfluorocarbonyl compounds, in particular of perfluoroketocarboxylic acid esters, perfluoroketocarboxylic acid halides and perfluorodiketones, the latter as far as possible to find two differently substituted keto groups.
  • the process should be generally applicable and provide the desired compounds in high yield and purity.
  • the first stage a) of the process according to the invention consists in the substitution of a hydrogen atom by a fluorosulfato group. Such substitution reactions are known for polyfluorinated compounds with a primary hydrogen atom (-CF 2 H).
  • the electrolysis can therefore be carried out in simple, undivided cells, wherein normal laboratory beaker cells can be used for the procedure according to the invention, without the invention being restricted to this.
  • Osmium, iridium, platinum or platinum alloys with approximately up to 10% of other noble metals, for example iridium, are suitable as anode.
  • the anode preferably consists of glassy carbon, which has proven to be particularly corrosion-resistant under the electrolysis conditions. Glassy carbon is also suitable as a cathode, although the question of the material is not critical for this electrode and other materials such as platinum, copper or stainless steel are also suitable.
  • vitreous carbon For the production, structure and properties of vitreous carbon, see for example the article «Thermal degradation of polymers to elemental carbon - a way to Materials of the future ”by E. Fitzer in Angew. Chem. 92, 375 to 386 (1980).
  • the area ratio of anode to cathode is between about 1: 1 to preferably about 5: 1 to 10: 1.
  • the base electrolyte which consists of fluorosulfonic acid and an alkali fluorosulfonate dissolved in it, it is advisable to dissolve a corresponding easily accessible alkali metal chloride, such as lithium chloride, sodium chloride or potassium chloride, in fluorosulfonic acid, which may have been subjected to purification beforehand by fractional distillation, the immediately Most of the hydrogen chloride escapes from the solution. The rest is driven off by introducing dry nitrogen.
  • the concentration of alkali metal sulfonate to be used in the base electrolyte is not critical and is preferably in the range from about 0.05 to about 3 moles per liter. Oxidizable impurities or traces of moisture may be removed by pre-electrolysis.
  • the monohydroperfluorocarbonyl compounds of the general formula required as starting materials are dissolved or dispersed in the base electrolyte, it being possible to use mixtures with up to about 60% by weight of monohydroperfluorocarbonyl compound, based on the base electrolyte.
  • the electrolysis is generally conducted at an anodic current density of about 10-150 mA - cm 2, preferably about 20-80 mA ⁇ cm -2 and a temperature of about 0 to 100 ° C, preferably about 20-40 ° C operated.
  • the electrolysis mixtures are worked up and the fluorosulfate operfluorocarbonyl compounds are isolated in a manner known per se.
  • fluoroorganic phase which contains only a little fluorosulfonic acid
  • the electrolysis product must be separated from the base electrolyte by distillation.
  • the electrolyte phase or the distillation bottoms can be recycled back into the electrolysis after adding fresh fluorosulfonic acid.
  • the crude fluorosulfate operfluorocarbonyl compounds II can be further purified by fractional distillation.
  • the carboxylic acid halide is placed in an inert solvent and, with cooling, a solution of the hydroxyl compound III in the same solvent is added.
  • the resulting hydrohalic acid is removed by washing with water.
  • the organic phase is separated off and distilled.
  • a suitable nucleophile alkali metal fluorides and / or aprotic N-bases
  • Chem. 18 3281 (1979) described decomposition of a secondary fluorosulfate performed. A rearrangement also occurs here: Also in Inorg. Chem. 5 2184 (1966) describes the decomposition of secondary fluorosulfates: While a large excess of cesium fluoride is used in the second case, no quantitative ratios are given in the first case. However, it must be assumed that, as usual, a more than equimolar amount of cesium fluoride is used per mole of fluorosulfate.
  • Alkali fluorides and / or aprotic nitrogen bases such as e.g. Triethylamine, 1,4-diazabicyclo [2.2.0] octane (DABCO) or 1.8-diazabicyclo [5.4.0] undec-7-ene (DBU) can be used.
  • the catalyst is preferably used in an amount of from about 1 to 50 mol percent, in particular from about 10 to about 30 mol percent, based on the compound IV to be decomposed.
  • reaction temperatures are between about -40 and + 120 ° C.
  • reaction can be carried out in an inert, aprotic solvent, but the procedure is preferably without a solvent.
  • reaction step c) it is practically irrelevant in which order the reaction components are added. However, it is advantageous to ensure thorough mixing of the batch throughout the reaction.
  • the catalyst and the fluorosulfate IV are combined and slowly heated until gas evolution occurs. After the evolution of gas has ended, the batch is distilled over a column.
  • ketocarbonyl compounds V produced by the process according to the invention are colorless and in some cases moisture-sensitive liquids. Therefore, the production must be carried out in the absence of moisture.
  • the electrolysis device consists of a cylindrical glass vessel provided with an outer cooling jacket and a lid and having an internal diameter of approximately 60 mm and a height of 100 mm.
  • the cell is equipped with a dry ice cooler which acts as a reflux cooler and also with a gas inlet cable, thermometer and the power supply for the electrodes.
  • the anode consists of a plate (100 ⁇ 20 ⁇ 3 mm) made of glass-like carbon, which is attached to the lid of the cell and about their surface immersed in the electrolyte.
  • a 1.5 mm thick platinum wire which is arranged at a distance of about 20 mm parallel to the anode, serves as the cathode.
  • the cell is cooled by an external cooling circuit with perchlorethylene as the cooling liquid. All parts of the device that come into contact with media are made of glass, platinum or PTFE.
  • the base electrolyte is prepared by adding 12.5 g (0.16 mol) of potassium chloride to 250 g of distilled fluorosulfonic acid; a colorless solution is formed, which is freed of residual hydrogen chloride by introducing dry nitrogen and then pre-electrolyzed at a current of 2 A for 4 hours.
  • electrolysis is carried out at a current of 2-3 A and a temperature of 20 ° C. until a charge of 88 Ah is reached.
  • the cell voltage is 6-16 V.
  • the organofluorine phase is separated from the electrolysis mixture and, after the addition of 50 g of fluorosulfonic acid, a further 141 g (0.71 mol) of 3-hydroperfluorobutanoic acid fluoride are added, and under the same conditions as before, up to a charge of 71 Ah electrolyzed.
  • the organofluorine phase is separated again by separation and fractionally distilled together with the first portion, giving 368 g (75% of theory) of 3-fluorosulfato-perfluorobutanoic acid fluoride, bp. 80-81 ° C.
  • Example 4 An electrolysis device as described in Example 4 is used and a base electrolyte as described in Example 1 is produced.
  • An electrolysis device as described in Example is used, but a plate (100x20x3mm) made of gaseous carbon is used as the anode and a platinum rod (diameter 1.5 mm, length 100 mm) is used as the cathode.
  • Example 2 An electrolysis device as described in Example 1 is used, but a rod (diameter 3 mm, length 100 mm) made of vitreous carbon is used as the cathode.
  • reaction is carried out in a fume cupboard.
  • a dry flask with magnetic stirrer, thermometer, reflux condenser and subsequent bubble counter 154 g (0.5 mol) are placed
  • the reaction is carried out in a fume cupboard.
  • the reaction is carried out in a fume cupboard.
  • the reaction is carried out in a fume cupboard.
  • the reaction is carried out in a fume cupboard.
  • the reaction is carried out in a fume cupboard.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Claims (2)

1. Procédé de préparation de composés poly- fluorocarbonylés de formule V:
Figure imgb0063
[dans laquelle R représente F, Clou un groupe perfluoroalkyle ayant 1 à 10, avantageusement 1 à 8, notamment 1 à 3 atomes de carbone, ou OR''', R'" étant un groupe alkyle, aryle ou aralkyle ayant avantageusement jusqu'à 10 atomes de carbone, notamment CH3 ou C2H5;
Rf est un groupe perfluoro alkyle ayant 1 à 10, avantageusement 1 à 8, notamment 1 à 3 atomes de carbone;
R'f est un groupe perfluoralkylène ayant 1 à 10, avantageusement 1 à 6, notamment 1 ou 2 atomes de carbone, et
n vaut 0 à 10, avantageusement 0 à 4, notamment 0 ou 1]

caractérisé en ce que:
a) on électrolyse des composés polyfluorocar- bonylés comportant encore un atome de H secondaire, de formule I:
Figure imgb0064
(dans laquelle Rf, R'f et n ont le même sens que pour la formule V, et
R" représente F, Clou un groupe perfluoroalkyle ayant 1 à 10, avantageusement 1 à 8, notamment 1 à 3 atomes de carbone), dans un électrolyte formé d'acide fluorosulfonique et d'un fluorosulfonate alcalin en utilisant du platine ou des métaux de la famille du platine (Os, Ir, Pt) et/ou du carbone vitreux comme matières d'anode et des matières usuelles, mais cependant stables dans les conditions de l'électrolyse, pour la cathode pour obtenir les composés fluorosulfato de formule II:
Figure imgb0065
(dans laquelle Rf, R'f, R" et n ont le même sens que pour la formule I),
b) on estérifie éventuellement, lorsque R" représente F ou CI, les composés fluorosulfato de formule II avec un composé organique hydroxylé de formule III:
Figure imgb0066
(dans laquelle R''' a le sens indiqué pour la formule V), et
c) on soumet les composés obtenus après les étapes de réaction a) et b), de formule IV:
Figure imgb0067
(dans laquelle R, Rf, R'f et n ont le même sens que pour la formule V) à une décomposition en présence de quantités catalytiques de fluorures alcalins et/ou de bases azotées aprotiques pour obtenir les composés de formule V.
2. Composés perfluorocarbonylés de formule IV:
Figure imgb0068
(dans laquelle Rf est un groupe perfluoroalkyle ayant 1 à 10, avantageusement 1 à 8, notamment 1 à 3 atomes de carbone,
R'f est un groupe perfluoralkylène ayant 1 à 10, avantageusement 1 à 6, notamment 1 ou 2 atomes de carbone,
R représente F, CI, un groupe perfluoroalkyle ayant 1 à 10, avantageusement 1 à 8, notamment 1 à 3 atomes de carbone, ou -OR''' (R"' étant un groupe alkyle, aryle ou aralkyle ayant avantageusement jusqu'à 10 atomes de carbone, notamment CH3 ou C2H5), et
n vaut 0 à 10, avantageusement 0 à 4, notamment 0 ou 1).
EP81107000A 1980-09-12 1981-09-07 Procédé pour la préparation de composés carbonyle polyfluorés et quelques représentants de cette famille de composés Expired EP0047948B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19803034491 DE3034491A1 (de) 1980-09-12 1980-09-12 Verfahren zur herstellung von polyfluorcarbonylverbindungen sowie einige neue vertreter dieser verbindungsklasse
DE3034491 1980-09-12

Publications (3)

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EP0047948A2 EP0047948A2 (fr) 1982-03-24
EP0047948A3 EP0047948A3 (en) 1982-05-05
EP0047948B1 true EP0047948B1 (fr) 1983-09-21

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US (2) US4524031A (fr)
EP (1) EP0047948B1 (fr)
JP (1) JPS5781434A (fr)
CA (1) CA1164887A (fr)
DE (2) DE3034491A1 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4686300A (en) * 1983-03-07 1987-08-11 E. I. Du Pont De Nemours And Company Polyfluoro gamma-ketoesters and 5-hydroxy gamma lactone analogues thereof
US4822897A (en) * 1983-03-07 1989-04-18 E. I. Du Pont De Nemours And Company Process for preparing polyfluoro γ-ketoesters and lactone isomers thereof
FR2582320B1 (fr) * 1985-05-21 1987-06-26 Atochem Procede electrochimique de preparation de derives organiques trifluoro (ou chlorodifluoro ou dichlorofluoro) methyles
JPH0788594B2 (ja) * 1986-07-31 1995-09-27 日本メクトロン株式会社 ヘキサフルオロアセトン水和物の製造法
CA1303062C (fr) * 1986-09-19 1992-06-09 Paolo Cuzzato Procede pour la preparation de fluorures de perfluoroacyle
GB2315268B (en) 1996-07-17 2000-05-10 Rh Ne Poulenc Chemicals Ltd Stabilization of perfluoroalkyl alkyl ketones
KR101249762B1 (ko) * 2012-06-13 2013-04-03 김성수 유연탄을 이용한 취사 및 난방용 고형 연료, 그리고 그 제조방법

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3847978A (en) * 1968-07-01 1974-11-12 Montedison Spa Perfluorinated linear polyethers having reactive terminal groups at both ends of the chain and process for the preparation thereof
US3651120A (en) * 1969-02-27 1972-03-21 Allied Chem Polyfluoroisoalkoxyalkyl sulfuric acids and salts thereof
DE2310426C2 (de) * 1973-03-02 1975-03-06 Farbwerke Hoechst Ag, Vormals Meister Lucius & Bruening, 6000 Frankfurt Hochfluorierte Xthersulfate und deren Verwendung als Egalisiermittel
JPS507054A (fr) * 1973-05-22 1975-01-24

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CA1164887A (fr) 1984-04-03
DE3034491A1 (de) 1982-04-29
JPS5781434A (en) 1982-05-21
EP0047948A2 (fr) 1982-03-24
DE3160970D1 (en) 1983-10-27
US4603017A (en) 1986-07-29
JPH0240652B2 (fr) 1990-09-12
US4524031A (en) 1985-06-18
EP0047948A3 (en) 1982-05-05

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